EXCHANGE 


A  Study  of  the  Reactions  of  Normal  Butyl 
Mercaptan  and  Some  of  its  Derivatives 


DISSERTATION 


SUBMITTED     TO    THE    BOARD    OF    UNIVERSITY    STUDIES    OF    THE 

JOHNS    HOPKINS   UNIVERSITY    IN    CONFORMITY  WITH  THE  RE- 

QUIREMENTS FOR  THE  DEGREE  OF  DOCTOR  OF  PHILOSOPHY 


BY 
THOS.  C.  WHITNER,  JR. 

June,  1920 


EASTON,  PA.; 

ESCHENBACH  PRINTING  COMPANY 
1921 


A  Study  of  the  Reactions  of  Normal  Butyl 
Mercaptan  and  Some  of  its  Derivatives 


DISSERTATION 


SUBMITTED    TO    THE    BOARD    OF    UNIVERSITY    STUDIES    OF    THE 
JOHNS    HOPKINS  UNIVERSITY    IN    CONFORMITY  WITH  THE  RE- 
QUIREMENTS FOR  THE  DEGREE  OF  DOCTOR  OF  PHILOSOPHY 


BY 

THOS.  C.  WHITNER,  JR. 
\* 

June,  1920 


EASTON,  PA.; 

ESCHENBACH  PRINTING  COMPANY 
1921 


CONTENTS 

Acknowledgment 2 

Introduction 3 

Experimental : 

Reactions  of  Butyl  Mercapto-ethyl  Alcohol 4 

Reactions  with  Alkyl  Halides 6 

Reactions  with  Aldehydes  and  Ketones 6 

Sulphones 7 

Mercuric  Iodine  Derivatives 8 

Discussion 9- 

Biography 10 


462004 


ACKNOWLEDGMENT. 

This  investigation  was  undertaken  at  the  suggestion  of  Professor  Reid 
and  carried  out  under  his  direction.  I  gladly  avail  myself  of  this  oppor- 
tunity to  express  to  him  my  sincere  appreciation  of  the  help  which  he 
gave.  I  wish  also  to  thank  Professors  Frazer,  Patrick,  and  Lovelace  for 
instruction  and  encouragement  received  from  them. 


A  SULFIDE  ALCOHOL,  OR  BUTYL  MERCAPTO-ETHYL 

ALCOHOL. 

In  a  recent  article  from  this  laboratory,1  the  acid,  CH3CH2CH2CH2- 
SCH2COOH,  was  studied  with  respect  to  the  influence  of  the  sulfur  atom 
on  the  chemical  and  physical  properties.    In  the  present  investigation, 
the    corresponding    alcohol,    CH3CH2CH2CH2SCH2CH2OH,    has    been 
studied  with  the  same  object  in  view. 

This  alcohol  is  obtained  readily  by  the  action  of  ethylene  chlorohydrine 
on  the  sodium  salt  of  butyl  mercaptan  in  water  solution.  It  is  a  color- 
less oil  boiling  at  92-3°  at  3  mm.  In  its  physical  properties  and  in  its 
reactions,  it  resembles  one  of  the  hgiher alcohols,  though  some  differences 
are  found.  Its  odor  suggests  a  higher  alcohol  and  a  sulfide,  though  the 
odor  of  its  acetate  is  much  more  like  that  of  an  acetate  of  a  higher  alcohol. 
The  chloride  and  bromide  are  readily  prepared  from  the  alcohol  by  the 
usual  methods,  but  it  shows  very  slight  tendency  to  combine  with  phthalic 
anhydride.  The  sulfur  atom  appears  to  exercise  somewhat  the  same 
influence  on  the  mobility  of  the  groups  in  the  0-position  as  in  the  sulfide 
acid  and  in  mustard  gas,  though  the  influence  is  less  evident  here.  The 
acetate  of  this  alcohol  is  stable,  while  the  diacetate  corresponding  to 
mustard  gas  is  very  unstable. 

From  the  bromide,  BuSCH2CH2Br,  the  sulfide,  BuSCH2CH2SBu,  was 
readily  obtained,  but  the  corresponding  sulfide  ether,  BuSCH2CH2OEt, 
could  not  be  prepared  by  heating  the  bromide  with  sodium  ethylate, 
vinyl-butyl  sulfide,  BuSCH  :  CH2,  was  formed  instead.  This  substance 
added  hydrobromic  acid  readily  to  give  the  original  bromide  instead  of  the 
secondary  bromide,  BuSCHBrCHg  which  we  desired. 

The  properties  of  the  alcohol  and  its  derivatives  are  brought  together 
in  the  following  table. 

TABLE  I. 

,0  ,25 

Compound.  B.  p.  <*<)•  ^25'         nD  20°. 

BuSCH,CHjOH 92-3°  at  3  mm.     0.9828  0.9693  1.4800 

BuSCH2CH,OCOCH, • 84°      at  4  mm.      1.0043  0.9875  1.4648 

BuSCHjCHjCl 68°      at  6  mm.     1.0315  1.0101  1.4825 

BuSCH2CH2Br 74°      at  3  mm.     1.2308  1.2089  1.6740 

1  Uyeda  and  Reid,  /.  Am.  Chem.  Soc.,  42,  2385  (1920). 


6 

Experimental. 

The  Alcohol,  Butyl  Mercapto-ethyl  Alcohol. — To  40  g.  of  caustic  soda  and  90  g. 
of  butyl  mercaptan  dissolved  in  250  cc.  of  water,  80  g.  of  chlorohydrine  was  added. 
The  mixture  was  boiled  under  a  reflux  condenser  for  one  hour  and  distilled  with  steam 
to  eliminate  impurities.  The  alcohol  remained  behind;  it  was  separated,  dried,  and 
distilled  in  vacuo.  Yield,  108  g. 

The  Acetate,  Butyl  Mercapto-ethyl  Acetate.— The  alcohol  was  mixed  with  an 
equal  amount  of  acetyl  chloride  and  the  mixture  allowed  to  stand  for  some  hours.  The 
product  was  washed  thoroughly  with  water,  then  dried  over  calcium  chloride  and  dis- 
tilled. 

Analysis.     Subs.,  1.7100:  0.5441  g.  KOH  required  for  saponification.   Calc. :  0.5448. 

The  Chloride,  Butyl  Mercapto-ethyl  Chloride. — A  mixture  of  30  g.  of  the  alcohol 
and  32  cc.  of  cone,  hydrochloric  acid  was  boiled  under  a  reflux  condenser  for  4  hours,  with 
the  further  addition  of  10  cc.  of  the  acid  during  this  operation.  The  mixture  was  ho- 
mogeneous at  first,  but  soon  separated  into  2  layers.  The  chloride  was  washed  thor- 
oughly, dried,  and  distilled. 

Analysis.     Calc.:  Cl,  23.25.     Found:  22.96. 

The  Bromide,  Butyl  Mercapto-ethyl  Bromide. — This  compound  was  prepared  in 
several  slightly  different  ways.  (1)  A  mixture  of  30  g.  of  the  alcohol  and  72  g.  (2  mole- 
cules) of  constant-boiling  hydrobromic  acid  was  boiled  for  8  hours;  yield,  13  g.  (2) 
Dry  hydrogen  bromide  was  passed  for  3  hours  into  50  g.  of  the  alcohol  which  was  kept 
cold;  yield,  20  g.,  or  27%.  (3)  Dry  hydrogen  bromide  was  passed  for  3  hours  into  a 
mixture  of  50  g.  of  the  alcohol  and  a  little  red  phosphorus  kept  at  a  temperature  of 
30-40°;  yield,  30  g.,  or  41%.  (4)  A  mixture  of  90  g.  of  the  alcohol  and  125  g.  of  con- 
stant-boiling hydrobromic  acid  (3.5  molecules)  was  boiled  for  3  hours  under  a  reflux 
condenser;  yield,  68  g.,  or  51%.  In  all  cases  the  layer  of  bromide  was  separated, 
washed  carefully,  and  distilled. 

Analysis.     Calc.:  Br,  40.57;  S,  16.28.     Found:  Br,  40.40;  S,  15.93. 

Dibutyl  Ethylene  Sulfide,  BuSCH2CH2SBu. — To  a  solution  of  5  g.  of  sodium 
in  100  cc.  of  alcohol,  20  g.  of  butyl  mercaptan  and  40  g.  of  the  bromide  just  described 
were  added.  The  mixture  was  refluxed  for  a  time,  water  was  added,  and  the  oily  layer 
was  separated,  dried  and  fractioned.  The  main  portion  boiled  at  130°  at  5  mm.  pres- 
sure and  proved  identical  with  a  product,  to  be  described  later,  which  was  obtained  by 
the  action  of  ethylene  bromide  upon  butyl  mercaptan. 

Vinyl-butyl  Sulfide. — To  75  cc.  of  alcohol  in  which  6  g.  of  sodium  had  been  dis- 
solved, 35  g.  of  the  bromide  was  added  and  the  mixture  was  heated  for  30  minutes. 
Water  was  added  and  the  oily  layer  washed  and  dried  .  Under  atmospheric  pressure, 
this  began  to  distil  at  150  °,  but  the  boiling  point  rose  steadily  to  217°.  Helfrich  and 
Reid1  had  a  similar  experience  with  vinyl  sulfide.  Several  preparations  were  made, 
but  no  material  of  constant  properties  could  be  obtained.  That  vinyl-butyl  sulfide 
was  present  seems  to  be  shown  by  the  following  experiments.  Bromine  was  absorbed 
rapidly  by  a  chloroform  solution  but  the  desired  dibromide  could  not  be  obtained; 
complicated  reactions  appear  to  take  place.  A  chloroform  solution  of  the  product 
was  saturated  with  hydrobromic  acid.  After  the  solution  had  stood  during  the  night, 
it  was  saturated  with  hydrogen  bromide  again.  When  the  chloroform  was  removed 
and  the  product  had  been  fractioned  in  vacuum,  an  oil' boiling  at  75°  under  4  mm. 
pressure  was  obtained,  d<J  1.2253,  and  dff  1.2075,  and  contained  40.38%  of  bromine 
instead  of  40.57  as  calculated  for  the  monobromide.  Since  the  density  does  not  agree 
with  that  of  the  original  primary  bromide,  it  was  hoped  that  it  might  be  the  secondary 

1  Helfrich  and  Reid,  J.  Am.  Chem.  Soc.,  42,  1225  (1920). 


bromide,  BuSCHBrCH3,  which,  according  to  Markownikow's  rule,1  would  be  expected. 
To  test  this  conclusion,  the  product  was  made  to  react  with  the  sodium  compound  of 
butyl  mercaptan  as  described  above.  A  bis-sulfide  was  obtained,  which  boiled  at  106-7° 
at  3  mm.  This,  on  oxidation,  gave  a  sulfone  melting  at  180°  which  is  known  to  be 
BuSO2CH2CH2SO2Bu,  instead  of  the  sulfone  (BuSO2)2CHCH3  which  melts  at  64°. 
This  showed  that  hydrobromic  acid  had  added  to  regenerate  some  at  least  of  the  orig- 
inal primary  bromide.  Since  the  yields  of  these  sulfones  are  always  low,  the  presence 
of  some  of  the  isomeric  bromide  is  not  excluded. 

The  Iodide. — An  attempt  was  made  to  obtain  this  compound  by  allowing  a  mixture 
of  15  g.  of  the  chloride,  20  g.  of  sodium  iodide  and  80  cc.  of  alcohol  to  stand  during  the 
night.  Water  caused  the  formation  of  an  oily  layer  which  was  washed,  and  dried  over 
calcium  chloride.  This  liquid  contained  41.89%  of  iodine' instead  of  52.02%  calculated 
for  the  iodide.  An  attempt  was  made  to  distil  it  in  vacua,  but  decomposition  took  place 
accompanied  by  deposition  of  iodine  on  the  sides  of  the  flask.  A  viscous  oil  was  left 
as  a  residue.  This  was  washed  with  a  solution  of  thiosulfate  and  the  iodine  in  the 
residual  oil  was  determined.  The  iodine  content  was  found  to  be  76.33%,  which  agrees 
with  76.48%  calculated  for  CJIgSI-jCH^CHjI,  though  this  agreement  is  regarded  as 
largely  accidental  in  view  of  the  properties  of  the  residue.  Rathke2  has  prepared  an 
analogous  compound,  (C2H6)2SIj.1 

The  peculiar  difficulty  encountered  with  the  iodide  may  be  related  to  the  known 
tendency  of  sulfides  to  form  sulfonium  compounds  with  alkyl  iodides.  A  complicated 
sulfone  might  be  formed  by  the  union  of  the  iodide  with  itself.  This  would  be  de- 
composed by  heat,  and  liberated  iodine  might  combine  with  some  of  the  iodide. 

Summary. 

The  following  compounds  have  been  prepared:  tt.C4H9SCH2CH2OH, 
butyl  mercapto-ethyl  alcohol;  w.C4H9SCH2CH2OCOCH3,  butyl  mercapto- 
ethyl  acetate;  tt.C4H9SCH2CH2Cl,  butyl  mercapto-ethyl  chloride;  w.C4H7- 
SCH2CH2Br,  butyl  mercapto-ethyl  bromide. 


SOME    DERIVATIVES    OF    BUTYL    MERCAPTAN    AND    THEIR 
MERCURIC  IODIDE  COMPOUNDS. 

Most  of  the  investigations  concerned  with  mercaptans  have  been  lim- 
ited almost  exclusively  to  the  lower  members  of  the  series,  viz.,  to  methyl 
and  ethyl  mercaptans.  The  following  investigation  was  undertaken  to 
extend  our  knowledge  to  the  higher  members  of  the  series,  particularly 
to  normal  butyl  mercaptan  and  to  accumulate  further  information  about 
compounds  which  contain  the  sulfide  grouping  more  than  once,  or  this 
group  with  other  groups. 

1  Ber.,  2,  660  (1869);  Ann.,  153,  256  (1870). 

2  Rathke,  Ann.,  152,  214  (1869). 


The  work  may  be  divided  into  2  parts:  compounds  prepared  by  the 
action  of  the  sodium  salt  of  butyl  mercaptan  with  halides;  and  those  pre- 
pared from  butyl  mercaptan  with  aldehydes  or  ketones. 

The  sulfones  of  these  sulfides,  as  well  as  their  mercuric  iodide  com- 
pounds, have  been  prepared,  partly  for  their  own  sakes  and  partly  to  fur- 
nish solids  for  identification  and  for  analysis. 

Experimental. 
Reactions  with  Halides. 

The  mercaptan  was  dissolved  in  from  3  to  5  parts  of  95%  alcohol, 
together  with  an  equivalent  amount  of  sodium  hydroxide,  and  to  this 
mixture  the  calculated  amount  of  the  halide  was  added.  The  mixture 
was  heated  till  the  reaction  seemed  to  be  complete,  diluted  with  water, 
and  the  oil  separated.  From  the  less  volatile  oils,  impurities  were  elim- 
inated by  steam  distillation.  The  oils  were  dried  over  calcium  chloride 
and  fractioned,  usually  in  vacuo.  It  is  hard  to  give  yields  on  account  of 
distillation  losses,  but  they  were  all  fairly  good.  The  halides  used  were 
ethyl  iodide,  methylene  chloride,  ethylene  bromide,  chloro-methylethyl 
ether  and  phenacyl  chloride.  The  following  compounds  have  been 
prepared:  ethylbutyl  sulfide;  methylene  dibutyl  sulfide  or  dibutyl  mer- 
capto-methane;  ethylene  dibutyl  sulfide  or  o;,/3-dibutyl  mercapto-ethane; 
ethoxy-methyl-butyl  sulfide;  and  butyl  phenacyl  sulfide.  Their  proper- 
ties are  given  in  Table  I. 

TABLE  I. 

jO  j25  ^200 

Formula.  B.  p.  °  C.  Q0.  n  D    . 

C2H6SC4H9  .......................     144-5  0.8763  0.8574  1.6527 

C4H9SCH2SC4H9  ..................     146  at  43  mm.  0  .9482  0  .9,332  1  .4964 

C4H9SCH2CH2SC4H9.  .  ..  ...........     129-30  at  5  mm.  0  .9524  0  .9389  1  .4962 

C2H5OCH2SC4H9  ..................     179-81  0.9054  0.8877  1.4502 

140  at  3  mm.  1.0712  1.0589  1.5050 


Reactions  with  Aldehyde  and  with  Ketones. 

The  reactions  of  butyl  mercaptan  with  aldehydes  and  with  ketones 
were  all  carried  out  under  the  same  conditions.  The  aldehyde,  or  ketone, 
was  mixed  with  2  equivalents  of  the  mercaptan  and  the  mixture  heated 
to  50-60  °  under  a  reflux  condenser  for  several  hours,  while  a  slow  current 
of  dry  hydrogen  chloride  was  passed  into  the  liquid.  With  acetaldehyde, 
application  of  heat  was  not  required.  Water  was  added  to  the  product, 
which  was  then  distilled  with  steam  to  rid  it  of  volatile  impurities.  The 
residual  oil  was  separated,  dried  over  calcium  chloride  and  fractioned  in 
vacuo.  The  yields  of  purified  products  were  50  to  60%  of  the  calculated 
amounts.  The  following  compounds  have  been  prepared:  acetaldehyde- 
dibutyl  mercaptal;  acetone-dibutyl  mercaptol;  benzaldehyde-dibutyl  mer- 
captol;  and  acetophenone  dibutyl  mercaptol.  Their  physical  properties 
are  given  in  Table  IT. 


9 
TABLE  II. 

Formula.  B.  p.  °  C.  dg.  da|.  «  D°°- 

CH3CH(SC4H9)j 105  at  3  mm.  0.9399  0.9272  1.4900 

(CH3)C(SC4H,)2 110  at  4  mm.  0.9304  0.9215  1.4842 

C6H6CH(SC4H9)j 167  at  4  mm.  1.0180  0.9999  1.4445 

C9H6CH3C(SC4H,), 167-8  at  3  mm.  1.0241  1.0110  1.5535 

Sulfones. 

Dibutyl  Sulfone  Methane,  CJ^SOzCHzSC^Hs.— Various  methods 
of  oxidation  were  tried,  but  none  was  found  entirely  satisfactory;  the  yields 
were  generally  poor. 

Four  g.  methylene  dibutyl  sulfide  was  added  to  150  cc.  of  water  con- 
taining 16  cc.  of  sulfuric  acid  and  25  g.  of  sodium  dichromate.  A  vigorous 
reaction  took  place,  after  which  the  mixture  was  boiled  for  45  minutes. 
As  the  liquid  cooled,  the  sulfone  separated.  After  recrystallization  from 
hot  water,  it  formed  large  white  plates.  The  same  product  was  obtained 
when  5  g.  of  the  sulfide  was  dropped  into  20  cc.  of  fuming  nitric  acid. 
The  sulfone  separates  when  this  mixture  is  poured  into  water.  The 
yield  was  about  2  g.  by  each  method.  The  melting  point  is  182°. 
Calc.:  S,  25.03.  Found:  25.06. 

Ethylene  Dibutyl  Sulfone,  CiHsSC^CHzCHzSOzCiHg.— Ten  cc.  of  the 
sulfide  was  added  slowly  to  20  cc.  of  fuming  nitric  acid,  while  the  acid 
was  cooled  and  stirred.  When  this  product  was  poured  into  water,  25 
g.  of  the  sulfone  separated.  Recrystallized  from  hot  water,  it  melted 
at  180°. 

Calc.  :  S,  23.73.    Found:  23.65. 

Ethylidene  Dibutyl  Sulfone,  CHsCHCSC^C^V—  While  a  suspension 
of  5  g.  of  the  sulfide  in  300  cc.  of  2%  sulfuric  acid  was  stirred  rapidly,  a 
5%  solution  of  potassium  permanganate  was  added  to  it  slowly  till  the 
pink  color  was  permanent;  then  sodium  sulfite  was  added  to  dissolve 
manganese  dioxide.  The  solution  was  evaporated  to  */»  its  volume, 
filtered  and  cooled.  This  caused  the  separation  of  the  sulfone  as  white 
needles.  It  melts  at  64°. 

Calc.:  S,  23.73.     Found:  23.97. 

Benzylidene  Dibutyl  Sulfone,  CeHaCHCSC^Hgk  was  prepared  by  the 
same  method.  Yield,  0.2  g.  from  5  g.  of  sulfide;  m.  p.,  86°.  A  better  yield 
(0.4  g  from  3  g.)  is  obtained  if  a  solution  of  the  sulfide  in  60  cc.  of  acetic 
acid  is  treated  first  with  water  until  an  incipient  turbidity  appears,  and 
then  slowly  with  pulverized  permanganate.  Occasionally  some  dil.  sul- 
furic acid  should  be  added.  When  the  calculated  amount  of  permanganate 
had  been  used  the  solution  was  diluted  with  100  cc.  of  water,  cooled  and 
filtered.  The  precipitate  was  extracted  with  boiling  water  from  which 
the  sulfone  crystallized  as  white  needles.  This  is  a  modification  of  the 
method  employed  by  Hilditch.1  No  sulfones  could  be  obtained  from 
1  Hilditch.  J  Chem.  Soc.,  93,  1524  (1908). 


10 

the  mercaptols  made  with  acetone  and  with  acetophenone ;  oxidation 
to  sulfonic  acids  must  have  taken  place.  When  the  sulfur  atoms  are  sep- 
arated by  2  carbon  atoms,  RSCH2CH2SR',  strong  oxidizing  agents  may  be 
used. 

Though  all  of  the  oxidation  methods  mentioned  above  were  tried  sul- 
fones  were  not  obtained  from  ethoxy-methyl-butyl  sulfide,  acetone-dibutyl 
mercaptal  and  acetophenone  dibutyl  mercaptol. 

Mercuric  Iodide  Derivatives. 

It  was  expected  that  mercuric  iodide  would  combine  with  these  sulfides 
1:1,  but,  except  for  the  2  sulfides,  methylene  dibutyl  sulfide  and  ethylene 
dibutyl  sulfide,  this  was  found  not  to  be  the  case.  In  all  other  cases  the 
ratio  of  iodine  to  mercury  in  the  product  was  less  than  2 : 1,  which  implies  that 
combination  takes  place  with  mercuric  rather  than  with  mercurous  iodide. 
Except  for  ethyl-butyl  sulfide,  2  mercuric  iodide  groups  are  taken  up  for 
each  atom  of  sulfur  present.  A  part  of  the  iodine  may  enter  the  molecule 
by  substitution  and  the  other  part  remains  in  the  mother  liquor  from 
which  the  compounds  separate.  In  a  number  of  instances  these  mother 
liquors  were  titrated  for  iodine  and,  in  all  cases,  very  nearly  the  calculated 
amount  of  iodine  was  found.  They  were  found  to  be  acid  to  litmus. 
The  mother  liquors  from  the  2  compounds  with  mercurous  iodide  men- 
tioned above,  contained  no  iodine. 

To  prepare  these  compounds,  2  to  5  g.  mercuric  iodide  was  suspended 
in  50  cc.  of  acetone,  and  the  sulfide  was  added  slowly  while  the  mixture 
was  shaken  and  cooled.  The  disappearance  of  red  mercuric  iodide  de- 
termined the  end  of  the  reaction.  This  required  about  2  mols  of  the 
sulfide  to  1  mol  of  the  mercuric  iodide  in  the  first  5  preparations  and  about 
1:1  for  the  other  4.  Sometimes  white  or  yellow  crystals  appeared  im- 
mediately, while  in  some  cases  the  addition  of  alcohol  was  necessary  to 
precipitate  the  compound. 

The  compounds  which  separated  readily  from  acetone  were  recrystal- 
lized  from  it,  the  others,  from  alcohol. 

The  compounds  and  their  analyses  are  given  in  Table  III. 

TABUJ  III. 

Hg  I 

Color  and  M.  p.       calc.       Pound.        calc.       Found. 

Compound.  form.  °  C.          %.  %.  %.  %. 

2C2H6SC4H9.3HgI white  plates  163  49.38  49.14  32.06    32.33 

C4H9SCH2SC4H9.HgIt small  cryst.  89  31 .02  30 .85  39 .26     39 .22 

C4HoSCH2CH,SC4H5.Hgl2 white  plates  85  30 .36  30 .41  

CsHeOCHISC^Hgl^ yellow  plates  156  43.16  43.42  40.98    41.17 

C«H6COCH2SC4H9(HgI)2 yellow  plates  158  46.48  46.60  29.41     29.67 

CH8CI(SC4H9)2(HgI)4 yellow  plates  138  48 .86  48 .83  38 .65    38 .44 

(CH2I)2C(SC4H9)2(HgI)4 yellow  plates  159  45.30  45.50  42.97     42.68 

CeH6CI(SC4H9)j(HgI)4 yellow  plates  86  47.08  47.17  37.23    36.93 

C6H§(CH2I)C(SC4H9)2(HgI)4 yellow  plates  155  46.72  46.84  36.93     36.75 

The  sulfur  in  (1)  was  found  to  be  5.05,  calc.  5.26%;  and  in  (4)  3.45,  calc.  3.33%. 


11 

Discussion. 

Phillips1  has  observed  that  methyl  sulfide  and  cupric  chloride  do  not 

form  (CH3)2S.CuCl2,  but  2(CH3)2S.2CuCl,  to  which  the  structural  for- 

CH3 


mula    CICu.S  -  S.CuCl  was  assigned,  since  there  is  no  indication  that 


CH3 

the  copper  has  been  reduced.  Similarly,  auric  chloride  unites  with  the 
same  sulfide  to  form  ClAu.S(CH3)2.  We  may  assume,  with  Phillips, 
that  the  sulfur  in  our  compounds  has  a  valence  of  4  and  write  : 

Hgl    CH3    Hgl 


Hgl    I         Hgl 

Tschugaeff2  has  obtained  crystalline  derivatives  of  the  type  CuCl  — 
RSCH2CH2SR  which  correspond  with  2  of  ours. 

The  only  compound  of  a  new  type  which  we  obtained  is  represented  by 
the  formula  2C2H6SC4H9.3HgI,  obtained  from  ethyl-butyl  sulfide,  which 
is  similar  to  2(CH3)2S.3HgCl2  obtained  by  Phillips,  except  that  in  this 
case  we  have  mercuric  iodide  instead  of  mercurous  iodide. 

Summary. 

A  number  of  derivatives  have  been  made  from  butyl  mercaptan.     The 
following  new  compounds  have  been  prepared : 
C2H5SC4H9,  2C2H5SC4H9.3HgI 
(C4H9S)2CH2,  (C4H9S02)CH2,  (C4H9S)2CH2.HgI2 
(C4H9SCH2)2,  (C4H9S02CH2)2,  (C4H9SCH2)2.HgI2 
C2H6OCH2SC4H9,  C2H5OCHISC4H9.  (Hgl)2 

C6H6COCH2SC4H9,  C6H5COCH2SO2C4H9,  C6H5COCH2SC4H9(HgI)2 
CH3CH(SC4H9)2,  CH3CH(SO2C4H9)2,  CH3CH(SC4H9)2(HgI)4 
(CH3)2C(SC4H9)2,  (CH2I)2C(SC4H9)2(HgI)4 
C6H5CH(SC4H9)2,  C6H5CH(S02C4H9)2,  C6H5CI(SC4H9)2(HgI)4 
C6H6(CH3)C(SC4H9)2,  C6H5(CH2I)C(SC4H9)2(HgI)4 

1  Phillips,  /.  Am.  Chem.  Soc.,  23,  256  (1901). 

2  Tschugaeff,  Ber.,  41,  2226  (1908). 


BIOGRAPHY. 

Thomas  Cobb  Whitner,  Jr.,  was  born  at  Atlanta,  Georgia,  February  7, 
1893.  His  elementary  education  was  received  in  the  schools  of  that  city. 
He  entered  the  Georgia  School  of  Technology  in  1909,  from  which  he  re- 
ceived the  degree  of  Bachelor  of  Science  in  Textile  Engineering  in  1914. 
Two  more  years  of  study  were  spent  at  this  same  institution  for  which  he 
received  the  degree  of  Bachelor  of  Science  in  Chemistry  in  1916.  In  1917 
he  entered  the  Johns  Hopkins  University  as  a  graduate  student  and  has 
continued  his  studies  in  Chemistry  at  this  University  for  the  past  three 
years. 


Gaylord  Bros. 

Makers 

Syracuse.  N.  V. 
PAT.  JAN.  21,1908 


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